Method of oxidizing heavy hydrocarbons



atented Aug, 31, 1926. p p P UNITED QFFIC.

JOSEPH HIDY JAMES OF PITTSBURGH, PENNSYLVANIA, AS$IGNOR TO CLARENCE P. BYRNES, TRUSTEE, OF SEWICKLEY, PENNSYLVANIA.

METHOD OF OXIDIZING HEAVY HYDBOCARBONS.

1N0 Drawing. Application filed December 8, 1921.. Serial No. 521,033;

In my copending applications, Serial Nos. lytic temperatures easier; and further, I 272,567 281,124; 335,940 and 435,355, Ihave find that, as noted in my earlier applicadescribedcertain methods and apparatus for tions, the bodies of higher molecular weight preparing intermediate partial oxidation are oxidized preferentially when in va or 5 products from hydrocarbons these products phase and in such a mixture. That is, t ey 60 belng in the range from a cohols through are oxidized more easily and in larger proaldehydes. to aldehyde acids. As pointed portion than the lighter hydrocarbons. out in said applications I may prepare these 'Afte'r condensing and recovering the products from any commercial source of aliproduct, the heavier oxidized products may phatlc hydrocarbons, such as petroleum, be removed from the mixture by precipita- 65 shale oil, the product from a low temperation, distillation or in any other desired ture distillate of coal tan-etc, manner. v p 1 In carrying out the said methods, there In an experimental run with my triple- .1s considerable difficulty in the proper vascreen catalytic apparatus, wax distillate (a porizing and treating of heavy hydrocarvery heavy fraction) gave trouble in at- 70 bons, and I have discovered that I can greattempting to vaporize it alone and pass the ly improve the method by mixing the very vaporthrough the catalytic screens. The heavy hydrocarbons such as wax distillate, temperature required for vaporization was pressure tar, heavy lubricating oil fractions, so high that considerable cracking, formavaselines, etc., with a lighter hydrocarbon tion on tarry products, and cloggingof the 7 before subjecting themto the partial oxidacatalytic material result. tion method. These heavy hydrocarbons The wax distillate was then mixed with have such high boiling points that I have an equal volume of gas oil (a lighter fracfound it diflicult to holdthe temperatures tion) and vaporized in the usual way and 425 of the catalytic layers down within the range-- mixed with air under the conditions fully 50 which insures proper yields and products? described in my other applications.

of good quality, this range being preferably In this run, 50% of wax distillate by from 230 to 450 C. Furthermore, if there volume was mixed with 50% of gas oil. The is a slight drop in temperature before the rate of oil feed was 100 cu. cm. per minute,

heavy vapors reach the catalytic screen or and the rate of water feed 25 cu. cm. per 85 screens, thereis danger of c ondensation and minute. The air fed to the first screen was clogging of the apparatus. Theaddition of 2 cu. ft. per minute; the air to the second steam as a diluent aids in overcoming this screen was 1 cu. ft. per minute; and the difliculty, but I may employ the present air to the third screen was.1% cu. ft. per

method either with or without the addition minute. The temperatures employed were 90 of steam. In this preferred method, the about 450 C. at each screen. heavy oil or fraction to be oxidized isfirst The total oilfeed was 14 liters, and the, mixed with a suitable proportion of a fractotal product recovered was 8 liters, being 2. tion of lower average molecular weight. 57% recovery. There was 30% of aldehyde 40 For example, wax, etc., may be mixed with fatty acids in the product, which also con 95 its own volume of gas oil or the wax may be tained about of aldehydes.

dissolved in suitable proportions of kerosene Better results than the above run can be or gas oil, using, heat, if necessary,to form obtained if a larger proportion ofthe lighter the solution or mixture. fraction is employed; especially as a lower 45 Such solution or mixture" is. then vaporconversion temperature can then be used. 100

ized, mixed with a regulated amount of air Furthermore, while the heavier hydrocarand passed, through a catalytic screen or bone are converted more easily than the screens in accordance with the processes set lighter hydrocarbons, yet both are partially forth in the applications above referred to. oxidized in this process.

I have found that with these mixtures I I may take the product from this proc- 10% can suiiiciently carry out my low temperaess', distil it up to about 300? (1, and em loy turej vapor phase oxidation of these heavy the distillate as a fuel for nternal 'com ushydrocarbons; this being due-to the fact tioiipengines. Theremalnlng heavier porthat the vaporization takes place at lower tion indistilling up to 300 C. can be contemperatures, rendering control of the cata verted into greases, soaps, lubricants, etc. 0

operate and more eflective in the treatment of heavier fractions.

The apparatus employed may be varied and various changes may be made ,in the process without departing from my invention, since I consider myself the first to mix a heavier hydrocarbon with a lighter fraction and subject the mixture to a partial oxidation method.

I claim:

1. In the partial oxidation of heavier mineral hydrocarbons, the steps consistin in mixing a heavier fraction of a mineral drocarbon with a lighter fraction of a minmama? eral hydrocarbon, vaporizing the mixture; and mixing it with oxygen and passing the vapor mixture through a reaction zone at a temperature within the partial oxidation range.

2. In the partial oxidation of heavier mineral hydrocarbons, the steps consisting in mixing a heavier fraction of a mineral hydrocarbon with a lighter fraction of a mineral hydrocarbon, vaporizing the mixture, and mixing it with oxygen and passing the vapor mixture through a reaction zone in contact with a-catalyst at a temperature within the partial oxidation range.

In testimony whereof I havehereunto set my hand.

JOSEPH HIDY JAMES. 

